CN104144965A - Poly(butylene-co-adipate terephthalate), method of manufacture, and uses thereof - Google Patents

Poly(butylene-co-adipate terephthalate), method of manufacture, and uses thereof Download PDF

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CN104144965A
CN104144965A CN201280071047.6A CN201280071047A CN104144965A CN 104144965 A CN104144965 A CN 104144965A CN 201280071047 A CN201280071047 A CN 201280071047A CN 104144965 A CN104144965 A CN 104144965A
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acid
poly
diester
combination
multipolymer
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CN104144965B (en
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胡斯努·艾尔普·艾利德代奥卢
加内什·卡纳安
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Saudi Basic Industries Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/12—Polyester-amides

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  • Life Sciences & Earth Sciences (AREA)
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  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

A method for preparing poly(butylene terephthalate-co-adipate)copolymer includes reacting (i) poly(butylene terephthalate-co-adipate)oligomers, wherein the oligomers comprise at least one polymer residue derived from a polyethylene terephthalate component and a quencher, with (ii) a chain extender under conditions sufficient to form the poly(butylene terephthalate-co-adipate)copolymer.

Description

Poly-(hexanodioic acid/butylene terephthalate), Its Preparation Method And Use
Background technology
Present disclosure relates to biodegradable aliphatics-aromatic copolyesters composition, and prepares the method for copolyesters and composition.These copolyesters and composition are useful as plastic article molding or that extrude, film and fiber.
Aliphatics-aromatic copolyesters is usually used in preparing biological degradable disposable goods.For example, United States Patent (USP) 6,020,393 disclose the random aliphatics-aromatic copolyesters of the side chain that is suitable for forming biological degradable disposable goods, and it comprises poly-(hexanodioic acid/butylene terephthalate), and (poly (butylene-co-adipate terephthalate) (PBAT).United States Patent (USP) 6,201,034 discloses by dimethyl terephthalate (DMT) (DMT) or terephthalic acid (TPA) and hexanodioic acid (AA) and has reacted with butyleneglycol (BDO) method of preparing PBAT.Biological degradability by gather (butylene terephthalate) (PBT) in the fusion of hexanodioic acid bring out.Therefore, polymkeric substance has approximately 109 ℃ of typical fusing point (T m), and the second-order transition temperature (Tg) between-25 ℃ to-30 ℃.For example titanium or tin compound carry out polymerization to adopt transesterification reaction (TE) catalyzer.
The inventor observes, and the biodegradable aliphatics-aromatic copolyesters product obtaining in such reaction is variable color, often from pink to red.This proposes a problem, the obstacle that uses polymkeric substance in end-use that becomes attractive in appearance of non-white polymer product, and wherein in end-use, the obvious and unavailable pigment of variable color, whitening agent or weighting agent easily overcome or hide.Further find, be difficult to maintain again or improve biodegradable aliphatics-aromatic copolyesters as other characteristics of satisfying the demand of PBAT realizing in white.Due at least aforesaid reason, still exist development to be prepared with the long-term unfelt needs of technique of the biodegradable aliphatics-aromatic copolyesters of use.
Summary of the invention
In embodiment, be provided for the method for preparation poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) (poly (butylene terephthalate-co-adipate)) multipolymer, the method is included in to be enough to form under the condition of gathering (terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer (i) poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer is reacted with (ii) chainextender, wherein this oligopolymer comprises by being selected from polyethylene terephthalate, at least one polymer residues that the polyethylene terephthalate component of polyethylene terephthalate copolymer and their combination is derivative and be selected from P contained compound, nitrogenous compound, the quencher of boron-containing compound and their combination, this chainextender is selected from poly-chlorinated isocyanurates, polymeric polyisocyanate, isocyanic ester and their combination, wherein multipolymer has the melt temperature of 100 ℃ to 120 ℃, the number-average molecular weight of at least 30,000g/mol, at least 1.0 limiting viscosity, the Tg of-30 ℃ to-10 ℃, and this multipolymer comprises the residue that is derived from polyethylene terephthalate component.
In another embodiment, the method that is poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer of 100 ℃ to 120 ℃ for the preparation of melt temperature comprises: be enough to form under the condition of poly-(hexanodioic acid fourth diester) oligopolymer, under the existence of catalyzer, make BDO and hexanodioic acid reaction; Be enough under the condition of depolymerization polyethylene terephthalate component poly-to form (terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer, in inert atmosphere, at the temperature of 190 ℃ to 270 ℃, at normal atmosphere or higher, 1, under the existence of 4-butyleneglycol, in poly-(hexanodioic acid fourth diester) oligopolymer, add polyethylene terephthalate component; Mole number based on catalyzer, to gathering the quencher that adds 0.05 to 1 molecular fraction in (terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer, quencher is selected from P contained compound, nitrogenous compound, boron-containing compound and their combination; And be enough to form under the condition of poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, oligopolymer is reacted with the chainextender of 0.01 to 5 molecular fraction, chainextender is selected from poly-chlorinated isocyanurates, polymeric polyisocyanate, isocyanic ester and their combination, the melt temperature of poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer is 100 ℃ to 120 ℃, and comprises at least one residue being derived by polyethylene terephthalate component.
Another prepares melt temperature is that the method for poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer of 100 ℃ to 120 ℃ comprises: being enough to the depolymerization of polyethylene terephthalate component, be under the condition of the first molten mixture, under the existence of catalyzer, in normal atmosphere or higher reactor, (i) polyethylene terephthalate component is reacted with (ii) diol component, polyethylene terephthalate component is selected from polyethylene terephthalate, the group of polyethylene terephthalate copolymer and their combination, diol component is selected from ethylene glycol, propylene glycol and their combination, being enough to form under the condition of the second molten mixture comprise oligopolymer, under the existence of catalyst component, in molten mixture, add BDO and hexanodioic acid, mole number based on catalyzer, to gathering the quencher that adds 0.05 to 1 molecular fraction in (terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer, quencher is selected from P contained compound, nitrogenous compound, boron-containing compound and their combination, and be under the condition of poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer of 100 ℃ to 120 ℃ being enough to form melt temperature, oligopolymer is reacted with the chainextender of 0.01 to 5 molecular fraction, chainextender is selected from chlorinated isocyanurates, polymeric polyisocyanate, isocyanic ester and their combination, and poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer comprises the residue being derived by polyethylene terephthalate component.
In another embodiment, it is poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer of 100 ℃ to 120 ℃ that melt temperature is provided, wherein multipolymer comprises following: the residue being derived by polyethylene terephthalate, and wherein polyethylene terephthalate is selected from polyethylene terephthalate, polyethylene terephthalate copolymer and their combination; Quencher residue; And the residue of the chlorinated isocyanurates of 0.05 to 1 weight percentage, polymeric polyisocyanate, isocyanic ester and their combination.
In another embodiment, composition comprises following: poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer; And at least one additive of selection from following: nucleator, antioxidant, UV stablizer, softening agent, epoxy compounds, melt strength additive, alcohol, acetic ester, alcohol-acetate copolymer, linking agent, antiaging agent, aging dose, antiblocking agent, water, odor control agent and their combination; And other thermoplastic polymer.
Describe a kind of goods, comprised composition described above.
A kind of method that forms goods comprises molding, coating, calendering, moulding or extrudes composition described above.
With reference to following explanation and claims, these and other feature, aspect and advantage will be understood better.
Embodiment
The inventor surprisingly finds that poly-(hexanodioic acid/butylene terephthalate) multipolymer that reacts preparation by poly-(hexanodioic acid/butylene terephthalate) oligopolymer with chainextender has superior property combination.In superior especially feature, by reacting with butyleneglycol (BDO) and carrying out reaction in－situ with hexanodioic acid and the second glycol, depolymerization aromatic polyester, especially, poly-(hexanodioic acid/butylene terephthalate) oligopolymer is prepared in polyethylene terephthalate homopolymer, multipolymer or their combination.The use in the aromatic carboxylic acid source of polyethylene terephthalate component allows the recycle of waste material polyester.Astoundingly, after oligopolymer forms, if add quencher to depolymerization mixture, even, under the existence of the residue from aromatic polyester, still obtain the superior characteristic of copolyesters.
As used herein, term " recycle " refers to manufacture and uses or for any component of waste material.Therefore therefore, recycle polyester can be the polyester having used, and the byproduct of for example beverage bottle, or manufacturing process does not for example meet required standard and by the byproduct that abandons or cancel.Therefore, recycle material can comprise the former green material of not utilized.The polyethylene terephthalate component of preparation aliphatics-aromatic copolyesters can be various ways.Conventionally, in PET example, PET component comprises thin slice, powder/fragment, film or spherical recycle (waste material) PET.Before use, the common processing treatment of PET to be to remove any impurity, as paper, and tackiness agent, polyolefine, polypropylene for example, polyvinyl chloride (PVC), nylon, poly(lactic acid) (aliphatic polyester) and other pollutent.
Prefix " biological " or " biologically-derived " represent that compound or composition are fundamentally derived from biogenic as used herein, biological example-1,3-PD is derived from biogenic (for example plant or microbial source) rather than petroleum source.Similarly, prefix " oil " or " petroleum derivation " represent that compound or composition are fundamentally derived from petroleum source, and for example, poly-(ethylene glycol terephthalate) of petroleum derivation is derivative by the reactant that itself is derived from oil.
Unless context in addition clearly regulation, singulative " a kind of/(a/an) " and " being somebody's turn to do " comprise plural object."or" represents "and/or"." combination wherein " is not restriction, and represents the component of at least one appointment, occurs together with the component of another kind of appointment or the component of similar quality.Unless further in addition regulation, as used herein, technology with scientific terminology have with the present invention under the general equivalent of understanding of those skilled in the art.Compound adopts modular system nomenclature to describe.For example, the optional position not replaced by the group of any indication is interpreted as having the valency that it is filled by indicated key or hydrogen atom.The dash "-" at two letters or between meeting is not for showing substituent tie point.For example ,-CHO connects by the carbon of carbonyl.
Term " random copolymers " refers to comprise macromolecular multipolymer as used in this application, and wherein in chain, the probability of the given monomeric unit of any given point discovery is independent of the character of adjacent cells.
Except being otherwise noted at operation embodiment or other, all numerals or the expression formula of the amount that refers to key element, reaction conditions etc. of using in this specification sheets and claim, be interpreted as by term " about ", being modified in all embodiments.Present patent application discloses various digital scopes.Because these scopes are continuous, they comprise each value between minimum value and maximum value.Narrate the terminal that the terminal of all scopes of identical feature or component can independent merging and comprised narration.Unless clearly stipulate in addition, the various digital scopes that illustrate in the application are approximation.The component of a certain amount of expression appointment of term " be greater than 0 to " to be to be greater than 0, and on reach to and comprise that the amount of higher appointment exists.
Unless specified otherwise herein, all ASTM test and data are from the < < U.S. ASTM standard yearbook > > of 2003 editions.
About term " terephthalic acid group ", " m-phthalic acid group ", " ethylene glycol group ", " butyleneglycol group " and " diethylene glycol group ", be used in reference to, for example, the weight percentage of group (wt%) in molecule, term " one or more m-phthalic acid group " represents to have formula (O (CO) C 6h 4(CO)-) group or the residue of m-phthalic acid, term " terephthalic acid group " represents to have formula (O (CO) C 6h 4(CO)-) group or the residue of m-phthalic acid, term " diethylene glycol group " represents to have formula (O (C 2h 4) O (C 2h 4the group of the glycol ether of)-) or residue, term " butyleneglycol group " represents to have formula (O (C 4h 8the group of the butyleneglycol of)-) or residue, and term " ethylene glycol group " represents to have formula (O (C 2h 4the group of the ethylene glycol of)-) or residue.
The butyleneglycol of copolyesters, hexanodioic acid or any other component can be derived by biogenic.In one embodiment, the butyleneglycol of all or part is derived from biogenic.As used herein, " biologically-derived glycol " refers to alcohol, except those appointments and by biogenic, for example, various pentoses, hexose etc. are derivative.
Poly-(hexanodioic acid/butylene terephthalate) multipolymer described here comprises hexanodioic acid group, butyleneglycol group and by the poly-derivative aromatic dicarboxylic acid group of (ethylene glycol terephthalate) component, i.e. polyethylene terephthalate homopolymer, polyethylene terephthalate copolymer or their combination.In other words, the depolymerization that poly-(hexanodioic acid/butylene terephthalate) multipolymer comprises by poly-(ethylene glycol terephthalate) is admixed to the aromatic dicarboxylic acid group in copolyesters.
The technique of preparing copolyesters under the existence of polyvalent alcohol by depolymerization aromatic polyester known in the art.For example, U.S. Patent number 5,451,611 have described by reacting conversion polyethylene terephthalate scrap with BDO for the technique of poly-(ethylene glycol terephthalate-altogether-Ding diester) (poly (ethylene-co-butylene terephthalate)) or polybutylene terephthalate.U.S. Patent number 5,451, the technique of 611 main purpose for providing direct switching through pet waste to become another kind of high value polymkeric substance, this technique does not have decomposed P ET to form monomer or oligopolymer for it.This patent discloses a lot of embodiment, and wherein multiple polymers has the combination of the glycol of measuring in varing proportions fusion.Patent 5,451,611 embodiment 11 shows by BDO and substitutes the PBT polymkeric substance that EG forms completely.U.S. Patent number 5,266,601 and U.S. Patent number 20090275698 (A1) described and by PET, reacted the technique of being prepared PBT by PET with BDO.
Therefore poly-(hexanodioic acid/butylene terephthalate) multipolymer comprises m-phthalic acid group, terephthalic acid group and their combination being derived by PET component.Copolyesters further comprises other residues that exist or that produce from depolymerization process in poly-(ethylene glycol terephthalate) component, it comprises following: from the catalyst residue of poly-(ethylene glycol terephthalate) component of preparation, the residue that comes additive residues in autohemagglutination (ethylene glycol terephthalate) component or side reaction to produce, wherein side reaction occurs in the reaction process of poly-(ethylene glycol terephthalate) component of preparation and/or BDO, hexanodioic acid and poly-(ethylene glycol terephthalate) component.For example, except butyleneglycol group, the glycol group that is admixed to copolyesters can be derived by arbitrary glycol, this glycol reacts with hexanodioic acid and aromatic dicarboxylic acid and forms copolyesters, for example, by following derivative group: ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 2,3-butyleneglycol, BDO, tetramethylcyclobutanediol, Isosorbide, cyclohexanedimethanol (comprise 1,2-CHDM, 1,3-cyclohexanedimethanol and 1,4 cyclohexane dimethanol), biologically-derived glycol, hexylene glycol and their combination.In another embodiment, glycol is selected from BDO, 1,3-PD, ethylene glycol and their combination.Such group for example, can produce from the polyethylene terephthalate component that comprises polyethylene terephthalate copolymer.
By the poly-derivative residue of (ethylene glycol terephthalate) component, can be ethylene glycol group, diethylene glycol group, antimony containing compounds, germanium-containing compound, titanium-containing compound, cobalt compound, sn-containing compound, aluminium, aluminium salt, 1,3-cyclohexanedimethanol isomer, 1,4-cyclohexanedimethanol isomer, an alkali metal salt, alkaline earth salt, P contained compound and negatively charged ion, sulfocompound and negatively charged ion, naphthalene dicarboxylic acids, 1,3-PD group or their combination.In one embodiment, the poly-derivative residue of (ethylene glycol terephthalate) component comprises ethylene glycol group, diethylene glycol group, and more particularly comprises the combination of ethylene glycol group and diethylene glycol group.
Therefore, in the embodiment the present invention includes, the independent key element and the combination that by the poly-derivative residue of (ethylene glycol terephthalate) component, comprise previous materials.In one embodiment, by the derivative residue of poly-(ethylene glycol terephthalate) component, comprise 1, the cis-isomeride of 3-cyclohexanedimethanol, 1, the cis-isomeride of 4-cyclohexanedimethanol, 1, the trans-isomer(ide) of 3-cyclohexanedimethanol, the trans-isomer(ide) of 1,4 cyclohexane dimethanol and their combination.In one embodiment, the combination that comprises ethylene glycol and diethylene glycol group by the poly-derivative residue of (ethylene glycol terephthalate) component, and can further comprise 1, the cis-isomeride of 3-cyclohexanedimethanol, 1, the cis-isomeride of 4-cyclohexanedimethanol, 1, the trans-isomer(ide) of 3-cyclohexanedimethanol, the trans-isomer(ide) of 1,4 cyclohexane dimethanol or their combination.In one embodiment, the cis-isomeride, the trans-isomer(ide) of cyclohexanedimethanol and their combination that by the poly-derivative residue of (ethylene glycol terephthalate) component, comprise ethylene glycol group, diethylene glycol group, cyclohexanedimethanol.In one embodiment, by the derivative residue of poly-(ethylene glycol terephthalate) component, comprise ethylene glycol group, diethylene glycol group and cobalt compound.Residue can multipolymer the total amount that is greater than 0 to 10 weight percentage exist, for example, 0.01 to 8 weight percentage of multipolymer, 0.05 to 6 weight percentage, 0.1 to 5 weight percentage, 0.1 to 2.5 weight percentage or 0.1 to 1.0 weight percentage.
Depolymerization is gathered (ethylene glycol terephthalate) component and forms the effective catalyzer of oligopolymer is known, and comprise, for example, tin compound, titanium compound and their combination and the in the literature combination of disclosed many other metal catalysts and metal catalyst.The specific examples that is used for the catalyzer of polymerization and/or transesterification reaction comprises antimony compounds, titanium isopropylate (titanium isopropoxide, titanium isopropoxide), oxalic acid manganese, weisspiessglanz, dibutyl tin acetate (dibutyl tin diacetate), zinc chloride or their combination.For obtain the speed of the depolymerization/oligomerization of satisfying the demand at required temperature, the amount of catalyzer can change, and can be determined by laboratory method.For example, the weight based on poly-(ethylene glycol terephthalate) component, the amount of catalyzer can be 1 to 1000ppm, 1 to 5000ppm or larger.In one embodiment, catalyzer is titanium isopropylate, and with trade name, TYZOR obtains from DuPont.
Depolymerization is gathered (ethylene glycol terephthalate) component and forms the effective condition of oligopolymer and can change, it depends on the considerations such as amount of concrete poly-(ethylene glycol terephthalate) component, its purity, catalyst type, reactant, and can be determined by laboratory method.For example, depolymerization can, under normal atmosphere or decompression and in inert atmosphere, be carried out at the temperature of 150 ℃ to 300 ℃.
Before reacting with chainextender, or when chainextender joins oligopolymer, with quencher, process poly-(hexanodioic acid/butylene terephthalate) oligopolymer.Quencher can be P contained compound, nitrogenous compound, boron-containing compound or their combination.
P contained compound comprises phosphoric acid, poly-(phosphoric acid), phosphorous acid, mono phosphoric acid ester butyl ester, dibutyl phosphate, mono alkyl phosphate, phosphate dialkyl ester and their combination.
Nitrogenous compound comprises alkylamine, aromatic amine, alkyl aromatic amine, alkanolamine, ammonium compound and their combination.
Boron-containing compound comprises boric acid, boron alkoxide, boron oxide compound (boric oxides), boron halogenide, metaborate, monoalkyl boron hydrochloric acid, dialkyl group borate, trialkylboron hydrochlorate, borazine (borazine) and their combination.
Conventionally, quencher is selected from phosphoric acid, phosphorous acid, boric acid and their combination.
In the embodiment of a method, the mole number based on catalyzer, joins quencher in poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer with the amount of 0.05 to 1 molecular fraction.In the embodiment of another method, based on total mole of terephthalic acid, hexanodioic acid and BDO, the amount of quencher is 0.05 to 1 molecular fraction.In one embodiment, the quencher residue that poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer contains 0.05 to 1 molecular fraction.
By making to gather (hexanodioic acid/butylene terephthalate) oligopolymer, react poly-(hexanodioic acid/butylene terephthalate) multipolymer of preparation with chainextender.In one embodiment, chainextender is selected from monokaryon isocyanic ester, double-core isocyanic ester, three core isocyanic ester, four core isocyanic ester or higher core isocyanic ester and their mixture, vulcabond choosing is the group of following composition freely: Toluene-2,4-diisocyanate, (tolylene 2 for 4-vulcabond, 4-diisocyanate), toluene 2, 6-vulcabond, 2, 4'-diphenylmethanediisocyanate, naphthylidene-1, 5-vulcabond, xylylene vulcabond, hexamethylene diisocyanate, isophorone diisocyanate, and methylene-bis (2-cyclic isocyanate hexane) (methylenebis (2-isocyanato cyclohexane)).
In one embodiment, chainextender is combination, and the gross weight based on combination, comprises: the chainextender that is selected from monokaryon isocyanide uraturia ester, the chainextender that contains two functional groups of reacting with oligopolymer end group or their combination of 45 to 80 weight percentage; The chainextender that is selected from double-core isocyanide uraturia ester, the chainextender that contains three functional groups of reacting with oligopolymer end group and their combination of 13 to 25 weight percentage; The chainextender that is selected from three core isocyanide uraturia esters, the chainextender that contains four functional groups of reacting with oligopolymer end group and their combination of 5 to 12 weight percentage; And four core isocyanic ester of 2 to 18 weight percentage or higher core isocyanic ester.
In the embodiment of a method, by making to gather (terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer, react preparation poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer with the chainextender of 0.05 to 5 weight percentage, wherein chainextender is selected from poly-chlorinated isocyanurates, polymeric polyisocyanate, isocyanic ester and their combination.In the embodiment of poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, the gross weight based on poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, chainextender residue can exist with 0.05 to 5 weight percentage.In another embodiment, chainextender can exist with the amount of 0.1 to 1 weight percentage.
The condition that oligopolymer known in the art reacts with chainextender, and condition depends on concrete reactant, their amount and required reaction times.For example, can in melt, carry out chain extension, for example under normal atmosphere or step-down in 100 ℃ to 120 ℃, selectively in inert atmosphere.
Poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer has superior property combination.For example, multipolymer can have the melt temperature of 105 ℃ to 125 ℃, 110 ℃ to 125 ℃, 100 ℃ to 120 ℃, 100 ℃ to 115 ℃ or 100 ℃ to 110 ℃.Multipolymer can have the Tg of-30 ℃ to-10 ℃ ,-25 ℃ to-10 ℃ or-20 ℃ to-10 ℃.
Can further prepare the multipolymer with requisite number average molecular weight, for example, be greater than 30,000g/mol, 30,000 to 300,000g/mol, 40,000 to 200,000g/mol or 45,000 to 150,000g/mol.
In addition, as at 23 ℃, in phenol/sym.-tetrachloroethane mixture that weight ratio is 60:40, measure, multipolymer can have be greater than 1.0 minutes Liter Per Minutes, be greater than 1.2 minutes Liter Per Minutes, be greater than 1.5 minutes Liter Per Minute (dL/ minute) I.V..
Particularly, multipolymer has the melt temperature of 100 ℃ to 125 ℃; The number-average molecular weight of at least 30,000g/mol; The limiting viscosity of 1.0dL/ minute (I.V.) at least; And the Tg of-30 ℃ to-10 ℃, and multipolymer comprises by the derivative residue of polyester residue component.Adjustable preparation condition is to realize required property combination.For example, multipolymer can have the melt temperature of 100 ℃ to 115 ℃; 40,000 to 200,000g/mol number-average molecular weight; The limiting viscosity of 1.2dL/ minute at least; And the Tg of-25 ℃ to-10 ℃.Other property combination within the scope of these are possible.
Except the copolyesters of foregoing description, composition comprises other components of being combined with copolyesters, other polymkeric substance and the additive of for example for moulding compound, filling a prescription.The example of polymkeric substance comprises aliphatic polyester, aromatic polycarbonate, aliphatic polycarbonate, starch, aromatic polyester, cyclic aliphatic polyester, polyesteramide and their combination etc.Polymkeric substance can be biologically-derived whole or in part, comprises the aromatic polyester of petroleum derivation and biologically-derived aromatic polyester.In this area, reported the chainextender for polyester, such as epoxide, bisoxazoline, two hexanolactam, dianhydride etc.In these chainextenders, due to the operability of epoxide relatively low cost and different structure, it is widely used in business scope most.
In concrete embodiment, copolyesters is combined with aliphatic polyester, for example poly-(lactic acid), poly-(hydroxyalkanoate), poly-(succinic acid fourth diester), poly-(hexanodioic acid fourth diester), poly-(succinic acid hexanodioic acid fourth diester) and poly-(caprolactone) (poly (butylene succinate adipate)) or their combination.Polyhydroxyalkanoate (PHA) is the straight chain polyester by the fermentation using bacteria generation of sugar or lipid at occurring in nature, and for example comprises, poly-(R-3-butyric ester) (PHB or poly-(3HB)).
In another embodiment, copolyesters is combined with aromatic polyester, for example, by 1 of petroleum derivation, poly-(the terephthalic acid propylene diester) that ammediol is derivative, by biologically-derived 1, poly-(the terephthalic acid propylene diester) that ammediol is derivative, by 1 of petroleum derivation, poly-(butylene terephthalate) that 4-butyleneglycol is derivative, by biologically-derived 1, poly-(butylene terephthalate) that 4-butyleneglycol is derivative, by poly-(ethylene glycol terephthalate) after use derivative poly-(terephthalic acid propylene diester), by poly-(ethylene glycol terephthalate) after use derivative poly-(butylene terephthalate), primary poly-(ethylene glycol terephthalate), poly-(ethylene glycol terephthalate) of recycle, with after poly-(ethylene glycol terephthalate), poly-(the terephthalic acid propylene diester) of recycle, the copolyesters of the recycle of terephthalic acid and ethylene glycol and cyclohexanedimethanol or their combination.
The amount of copolyesters and additive depends on the desired characteristic of Biodegradable composition and is different.In one embodiment, the gross weight based on composition, additive exists with the amount of 2 to 90 weight percentage, for example from 2 to 40 weight percentage or from 40 to 90 weight percentage.When copolyesters and starch are used, the gross weight of the composition based on whole, the amount of starch can be in the scope of 40 to 90 weight percentage, and the amount of polyester can be in from 10% to 60% scope.When copolyesters is combined with poly(lactic acid), the gross weight based on composition, the amount of polyester can be within the scope of 40 to 90 weight percentage and the amount of poly(lactic acid) can be in the scope of 10 to 60 weight percentage, 40 to 60 weight percentage particularly.
Gross weight based on composition, composition also can contain the additive of 0.01 to 45 weight percentage, and wherein additive is selected from alcohol, acetic ester, alcohol-acetate copolymer and their combination.In addition, the weight based on composition, composition can contain the additive of from 0.01 to 2 weight percentage, and wherein additive is selected from linking agent, antiaging agent, aging dose, antiblocking agent, water, odor control agent and their combination.
Conventionally can use the additive being admixed in polymer composition, its prerequisite is for to select additive, so that characteristic that can be not required to composition, for example, biological degradability, surging force, flexural strength, color etc. produce remarkable adverse influence.Such additive can mix under with the time suitable in forming the process of composition at blending ingredients.Feasible additive comprises impact modifying agent, filler, toughener, antioxidant, thermo-stabilizer, photostabilizer, ultraviolet ray (UV) absorption agent, softening agent, lubricant, releasing agent, static inhibitor, tinting material, whipping agent, fire retardant, anti-dripping agent and stable radiation agent.Can use the combination of additive, for example antioxidant, UV absorption agent and releasing agent.Gross weight based on composition, the total amount of additive (not being arbitrary impact modifying agent, filler or toughener) is generally 0.01 to 5 weight percentage.In embodiment, can use nucleator, antioxidant, ultra-violet stabilizer, softening agent, epoxy compounds, melt strength additive or their combination of 0.01 to 5.00 weight percentage.
Advantageously, copolyesters can be biodegradable with the composition that contains copolyesters.This represents that copolyesters and the composition that contains copolyesters present aerobic biological degradation, as ISO 14855-1:2005 measures.As everyone knows, SO14855-1:2005 has stipulated the measuring method of the final aerobic biological degradation of plastics, based on organic compound, under the composting conditions of controlling, by amount and the plastics disintegration of the carbonic acid gas in the last measurement formation of test.Design the method is in order to simulate the typical aerobic composting condition for the organic composition of solids mixing municipal wastes.Test materials is exposed to the inoculum that derives from compost.Compost has replaced environment, wherein monitors nearly and control temperature, ventilation and humidity.Design experiment method is in order to show that the carbon in test materials is converted into percentage conversion and the conversion rate of the carbonic acid gas of release.Also stipulated the variant of the method, adopted the mineral bed (vermiculite) of inoculation thermophilic microorganism to replace the compost becoming thoroughly decomposed, wherein thermophilic microorganism obtains from have the compost of specific activation section.Designing this variant is in order to draw percentage ratio and the conversion rate of the carbon that is converted into carbonic acid gas in substances.Conventionally, our copolyesters (with the composition that contains copolyesters) presents after 75 days at least 30% biological degradation (to be converted into CO 2the % of the test subject solid carbon of the gaseous state of form, mineral carbon measures).In one embodiment, copolyesters (with the composition that contains copolyesters) presents after 75 days at least 40% or 50% biological degradation.The biodegradable scope of copolyesters (with the composition that contains copolyesters) can be from least 30% to 50% or at least 30% to 60% or at least 30% to 70%.
Advantageously, can manufacture practical goods by copolyesters and the composition that contains copolyesters.In embodiment, goods can be extruded by multipolymer or the composition that contains multipolymer, calendering, extrusion molding, blowing, solvent casting or injection molding.Goods can be film or thin plate.When goods are film, goods can form by extrusion molding or the composition that rolls copolyesters or contain copolyesters.In other application, for example, in film packaging application, copolyesters and the composition that contains copolyesters are practical to film.
Embodiment 1: a kind of method for the preparation of poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, the method is included in to be enough to form under the condition of poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, (i) poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer is reacted with (ii) chainextender, wherein oligopolymer comprises at least one polymer residues and the quencher being derived by polyethylene terephthalate component, polyethylene terephthalate component is selected from polyethylene terephthalate, polyethylene terephthalate copolymer and their combination, quencher is selected from P contained compound, nitrogenous compound, boron-containing compound and their combination, wherein chainextender is selected from poly-chlorinated isocyanurates, polymeric polyisocyanate, isocyanic ester and their combination, wherein poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer has the melt temperature of 100 ℃ to 120 ℃, the number-average molecular weight of at least 30,000g/mol, the limiting viscosity of at least 1.0 minutes Liter Per Minutes, the Tg of-30 ℃ to-10 ℃, and multipolymer comprises the residue being derived by polyethylene terephthalate component.
Embodiment 2: the method in embodiment 1, comprise that (a) is being enough to form under the condition of poly-(hexanodioic acid fourth diester) oligopolymer, under the existence of catalyzer, make BDO and hexanodioic acid reaction; (b) be enough under the condition of depolymerization polyethylene terephthalate component poly-to form (terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer, in inert atmosphere, at the temperature of 190 ℃ to 270 ℃, normal atmosphere or more relative superiority or inferiority, 1, under the existence of 4-butyleneglycol, polyethylene terephthalate component is combined with poly-(hexanodioic acid fourth diester) oligopolymer; And (c) mole number based on catalyzer, to the phosphoric acid quencher that adds 0.05 to 1 molecular fraction in poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) polymkeric substance.
Embodiment 3: embodiment 1 or 2 method, comprise that (a) is under the condition of the first molten mixture being enough to depolymerization polyethylene terephthalate component, under the existence of catalyst component, in normal atmosphere or higher reactor, (i) polyethylene terephthalate component is reacted with (ii) diol component, wherein, polyethylene terephthalate component is selected from the group of polyethylene terephthalate, polyethylene terephthalate copolymer and their combination, and diol component is selected from ethylene glycol, propylene glycol and their combination; And (b) being enough to form under the condition of the second molten mixture comprise oligopolymer, under the existence of catalyst component, in molten mixture, add BDO and hexanodioic acid; And (c) mole number based on catalyzer, to the phosphoric acid quencher that adds 0.05 to 1 molecular fraction in poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer.
Embodiment 4: a kind of is the method for poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer of 100 ℃ to 120 ℃ for the preparation of melt temperature, the method comprises, be enough to form under the condition of poly-(hexanodioic acid fourth diester) oligopolymer, under the existence of catalyzer, make BDO and hexanodioic acid reaction; Be enough under the condition of depolymerization polyethylene terephthalate component poly-to form (terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer, in inert atmosphere, at 190 ℃ to 270 ℃ temperature, normal atmosphere or more relative superiority or inferiority, 1, under the existence of 4-butyleneglycol, in poly-(hexanodioic acid fourth diester) oligopolymer, add polyethylene terephthalate component; Mole number based on catalyzer, to gathering the phosphoric acid quencher that adds 0.05 to 1 molecular fraction in (terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer; And be enough to form under the condition of poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, oligopolymer is reacted with the chainextender of 0.01 to 5 weight percentage, wherein, chainextender is selected from poly-chlorinated isocyanurates, polymeric polyisocyanate, isocyanic ester and their combination, poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer has the melt temperature of 100 ℃ to 120 ℃, and comprises at least one residue being derived by polyethylene terephthalate component.
Embodiment 5: a kind of is poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer of 100 ℃ to 120 ℃ for the preparation of melt temperature, the method comprises, being enough to the depolymerization of ethylene glycol terephthalate component, be under the condition of the first molten mixture, under the existence of catalyst component, in the reactor of normal atmosphere or larger pressure, (i) polyethylene terephthalate component is reacted with (ii) diol component, wherein polyethylene terephthalate component is selected from polyethylene terephthalate, the group of polyethylene terephthalate copolymer and their combination, diol component is selected from ethylene glycol, propylene glycol and their combination, being enough to form under the condition of the second molten mixture comprise oligopolymer, under the existence of catalyst component, in molten mixture, add BDO and hexanodioic acid, mole number based on catalyzer, to gathering the quencher that adds 0.05 to 1 weight percentage in (terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer, and be enough to form under the condition of poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, oligopolymer reacts with the chainextender of from 0.01 to 5 weight percentage, chainextender is selected from chlorinated isocyanurates, polymeric polyisocyanate, isocyanic ester and their combination, the melt temperature of poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer is 100 ℃ to 120 ℃, and comprises the derivative residue of polyethylene terephthalate component.
Embodiment 6: the method for any one in above-mentioned embodiment, wherein poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer has at least 30,000 molecular weight; The limiting viscosity of at least 1.0 minutes Liter Per Minutes; Tg with-30 ℃ to-10 ℃.
Embodiment 7: the method for any one in above-mentioned embodiment, the total mole number based on terephthalic acid, hexanodioic acid and BDO wherein, the amount of quencher is from 0.05 to 1 molecular fraction.
Embodiment 8: the method for any one in above-mentioned embodiment, wherein quencher is selected from phosphoric acid, phosphorous acid, boric acid, nitrogenous compound and their combination.
Embodiment 9: the method for any one in above-mentioned embodiment, wherein chainextender is selected from monokaryon isocyanic ester, double-core isocyanic ester, three core isocyanic ester, four core isocyanic ester or higher core isocyanic ester and their mixture, vulcabond choosing is the group of following composition freely: Toluene-2,4-diisocyanate, 4-vulcabond, Toluene-2,4-diisocyanate, 6-vulcabond, 2, 4'-diphenylmethanediisocyanate, naphthylidene-1, 5-vulcabond, xylylene vulcabond, hexamethylene diisocyanate, isophorone diisocyanate, and methylene-bis (2-cyclic isocyanate hexane).
Embodiment 10: the method for embodiment 9, wherein chainextender is combination, gross weight based on combination, it comprises: the chainextender that is selected from monokaryon isocyanic ester, contains two functional groups of reacting with oligopolymer end group of 45 to 80 weight percentage or the chainextender of their combination; The chainextender that is selected from double-core isocyanic ester, contains three functional groups of reacting with oligopolymer end group of 13 to 25 weight percentage and the chainextender of their combination; The chainextender that 5 to 12 weight percentage are selected from three core isocyanic ester, contain four functional groups of reacting with oligopolymer end group and the chainextender of their combination; And four core isocyanic ester of 2 to 18 weight percentage or higher core isocyanic ester.
Embodiment 11: the method for any one in above-mentioned embodiment, wherein glycol is selected from ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 2,3-butanediol, BDO, tetramethylcyclobutanediol, Isosorbide, hexylene glycol, 1,3-cyclohexanedimethanol isomer, 1,4 cyclohexane dimethanol isomer, biologically-derived glycol or their combination.
Embodiment 12: the method for any one in above-mentioned embodiment, wherein glycol is selected from BDO, 1,3-PD, ethylene glycol and their combination.
Embodiment 13: the method for any one in above-mentioned embodiment, wherein aromatics dicarboxylic compounds is selected from terephthalic acid or its two (C1-3) alkyl ester, m-phthalic acid or its two (C1-3) alkyl ester, naphthalic acid or its two (C1-3) alkyl esters and their combination.
Embodiment 14: the method for any one in above-mentioned embodiment, wherein aromatic dicarboxylic acid compound is terephthalic acid or its two (C1-3) alkyl ester.
Embodiment 15: the method for any one in above-mentioned embodiment, wherein polyester components residue comprises the residue of dimethyl isophthalate, cyclohexanedimethanol, ethylene glycol, glycol ether, triglycol, ethylene glycol group, diethylene glycol group, m-phthalic acid group and their combination.
Embodiment 16: a kind of melt temperature is poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer of 100 ℃ to 120 ℃, wherein multipolymer comprises the residue that is derived from polyethylene terephthalate component, and polyethylene terephthalate component is selected from polyethylene terephthalate, polyethylene terephthalate copolymer and their combination; Quencher residue; And the residue of the chlorinated isocyanurates of 0.05 to 1 weight percentage, polymeric polyisocyanate, isocyanic ester and their combination.
Embodiment 17: the multipolymer of embodiment 16, based on poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, the quencher residue that comprises 0.05 to 1 molecular fraction.
Embodiment 18: embodiment 16 or 17 multipolymer, wherein the derivative residue of polyethylene terephthalate component is selected from ethylene glycol group, diethylene glycol group, m-phthalic acid group and their combination.
Embodiment 19: the multipolymer of any one in above-mentioned embodiment, wherein, based on poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, multipolymer comprises the ethylene glycol group that is less than 10 molecular fractions.
Embodiment 20: the multipolymer of any one in above-mentioned embodiment, wherein, based on poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, multipolymer comprises the m-phthalic acid ester group that is less than or equal to 2 molecular fractions.
Embodiment 21: the multipolymer in above-mentioned embodiment described in any one, wherein based on poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, the combination that multipolymer comprises the ethylene glycol group and the m-phthalic acid ester group that are less than 10 molecular fractions.
Embodiment 22: composition comprises following material: poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer of any one of the claims; With at least one additive that is selected from the following: nucleator, antioxidant, UV stablizer, softening agent, epoxy compounds, melt strength additive, alcohol, acetic ester, alcohol-acetate copolymer, linking agent, antiaging agent, aging dose, antiblocking agent, water, odor control agent and their combination; And other thermoplastic polymer.
Embodiment 23: the composition of embodiment 22, it comprises every: the gross weight based on composition, is greater than poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymers of 10 to 59.99 weight percentage; Gross weight based on composition, is greater than 40 to the polymkeric substance that is less than 89.99 weight percentage, and polymkeric substance is selected from aliphatic polyester, aliphatic polycarbonate, starch, aromatic polyester, present cycloaliphatic polyesters, polyesteramide, aromatic polycarbonate and their combination; And the gross weight based on composition, being greater than the additive of 0.01 to 5 weight percentage, additive is selected from nucleator, antioxidant, UV stablizer, softening agent, epoxy compounds, melt strength additive and their combination; Gross weight based on composition, the additive of from 0.01 to 45 weight percentage, additive is selected from alcohol, acetic ester, alcohol-acetate copolymer and their combination; And the gross weight based on composition, the additive of 0.01 to 2 weight percentage, additive is selected from linking agent, antiaging agent, aging dose, antiblocking agent, water, odor control agent and their combination.
Embodiment 24: embodiment 22 or 23 composition, wherein aliphatic polyester is selected from poly-(lactic acid) class, poly-(hydroxyalkanoate) class, poly-(succinic acid fourth diester) class, poly-(hexanodioic acid fourth diester) class, poly-(succinic acid hexanodioic acid fourth diester) class, poly-(caprolactone) class and their combination.
Embodiment 25: a kind of goods of the composition that comprises root embodiment 22,23 or 24.
Embodiment 26: the goods of embodiment 25, wherein goods be moulded product, film, fiber or coating (coating, coating).
Embodiment 27: a kind of method that forms goods, comprises molding, coating, calendering, moulding or extrude the composition of embodiment 22,23 or 24.
As mentioned above, can adopt the different combination of aforesaid embodiment.The present invention has further described following illustrative embodiment, and wherein unless specified otherwise herein, all umbers and percentage ratio are by weight.
Embodiment
material
Under classify the inventory in the material that adopts in embodiment, abbreviation and selection source as.
ADA: hexanodioic acid (from INVISA)
BDO:1,4-butyleneglycol (from BASF, 99.5 weight percentage pureness specifications)
Phosphoric acid: phosphoric acid (from Acros, grade/purity 98%)
TPT: titanium isopropylate (from DuPont, business Tyzor grade)
Be total to-adipic acid ester of PBT-: poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) (Poly (butylene terephthalate-co-adipate))
PET: poly-(ethylene glycol terephthalate)
The PET of recycle: the PET that is located at thin slice that the commercial supplier of India obtains or spherical recycle from general headquarters.
method and program
L*, a*, the b* value of report obtain by the diffuse-reflectance method of obtaining on the Gretag Macbeth Color-Eye7000A with D65 illumination.Term " white " as used in this application, represent that being described as white material presents L* value, it is at least 75, at least 80 or at least 85, corresponding one group " a " and " b " value approach 0 substantially, (on CIE color scale (CIE color scale), being less than 5 units), wherein at CIE LAB color scale (CIE LAB color scale), " a " represents that the redness of white material and green tone and " b " value represent blueness and the yellow tone of white material.L* value can be in the scope from 75 or 75 or 85 to 100." L*, a, b " method of describing color is well-known, and is set up by CIE (International Commission on Illumination).By limiting illumination CIE, provide colorimetry suggestion, viewer and for obtaining describing method that color 3 sits target values for being positioned at the color of color space, it is represented by L*, a, b.When expressing color in CIELAB, L* stipulates brightness, if value is close to 0, represents that how dark hypersorption or color have.If L* close to 100, represents that how shallow total reflection or color have.A* indication color has how green or red, and b* representative color has many indigo plant or yellow.
Limiting viscosity (I.V.) is by Viscotek 500 is that Relative Viscometer Y501 measures.In typical technique, the polymer samples of 0.5000 gram is fully dissolved in 60/40 mixture (volume ratio) of phenol/sym.-tetrachloroethane solution (Harrell Industries).
Dynamic scan calorimetry (DSC), adopts the Perkin Elmer DSC 7 that Pyris DSC 7 softwares are housed to measure the synthetic melting characteristic of polymkeric substance and the thermal property of corresponding monomer.In typical technique, polymer samples (10-20mg) is heated to 200 ℃ (20 ℃/min) from-50 ℃, at 200 ℃, keeps 1min, cools back to-50 ℃ (20 ℃/min), then at-50 ℃, keep 1min, and repeat above-mentioned heating/cooling cycle.The second heating bout is commonly used to obtain T gand T mdata.
Embodiment 1
The object of embodiment 1 for prepare polyester PBT-altogether-adipic acid ester, its adopt phosphoric acid as catalyst quenchers and hexamethylene diisocyanate as chainextender, by the PET use, hexanodioic acid (ADA) and BDO (BDO), derived.Material, amount and reaction conditions are shown in table 1.
The material of table 1. embodiment 1 and condition
technology and program
First, the ADA of the BDO of 50 grams and 36.5 grams is introduced in three neck round-bottomed flasks.Reactor is placed in the oil bath that temperature is adjusted to 175 ℃.Then, the TPT of 250ppm joins in the reactor under inert atmosphere.Transesterification temperature rises to 220 ℃ with the speed of 2 ℃/min, stirs under nitrogen with 260rpm simultaneously.Water under reduced pressure, distills out excessive butyleneglycol after forming and stopping.Then by 48 grams, with the PET crossing and 50 grams of BDO, introduce reactor, at 220 ℃, stir simultaneously.Mixture heating surpasses 2 hours time-histories.Then, the phosphoric acid solution in water (0.1g/ml) that adds 0.5ml.The temperature of reaction mixture rises to 240 ℃.When all PET thin slices are all during melting, vacuum is brought down below 1 torr.Obtain after required oligopolymer, stop vacuum and to the hexamethylene diisocyanate that adds 0.7ml in reactor.Under nitrogen atmosphere, melt mixes with hexamethylene diisocyanate 15 minutes.Obtain after required limiting viscosity stopped reaction.
result
Table 2 shows Tg, Tm, molecular weight data (adopt polystyrene standards, from gel permeation chromatography (GPC), obtain), limiting viscosity (I.V.) and from the macroscopic color of embodiment 1.
The result of table 2. embodiment 1
Table 3 has been described the proximate analysis of the embodiment 1 obtaining by proton N MR.The report therefore numeral in road has reflected the combination degree of designating unit in polymkeric substance.
Table 3. embodiment 1 proximate analysis result
discuss
(approach approach) has been prepared the derivative PBAT copolyesters by the PET using to adopt novel method.The method comprises: first, under the existence of phosphoric acid catalyst quencher, prepare the oligopolymer of PBAT by the melt phase polycondensation of ADA, BDO and PET.Due to low reaction temperatures and successfully catalyzer quencher, consequent oligopolymer is rendered as white.Secondly, at identical temperature and normal atmosphere, adopt hexamethylene diisocyanate by oligopolymer chain extension.In 15 minutes, observe the sharply increase of viscosity, it shows to be fast and to be quantized by the chain extension of hexamethylene diisocyanate.
Result proved technique shown in table 2 can make copolyesters obtain very high IV.Be total to-adipic acid ester (T of PBT-with the business obtaining from BASF printed data table m=117 ℃) to compare, the melt temperature of embodiment 1 is low 15 ℃.
Consequent copolyesters comprises m-phthalic acid and EG in its trunk, and its PET by recycle produces.Compare be total to-adipic acid ester of the PBT-being prepared by PET by other techniques, in trunk, the molecular fraction of EG is high, and this may be due to vacuum degree deficiency in chain extension technique.
Here all document full contents of quoting are to be incorporated to herein with reference to mode.Although set forth exemplary embodiment for illustrative object, above-mentioned explanation should not thought limitation of the scope of the invention.Therefore, those skilled in the art can expect making without departing from the spirit and scope of the present invention various modifications, variation and replacement.

Claims (27)

1. for the preparation of a method for poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, described method is included in to be enough to form under the condition of described poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, makes the following reaction:
(i) poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer, wherein said oligopolymer comprises:
By at least one the derivative polymer residues of polyethylene terephthalate component that is selected from polyethylene terephthalate, polyethylene terephthalate copolymer and their combination, and
Be selected from the quencher of P contained compound, nitrogenous compound, boron-containing compound and their combination, with
(ii) chainextender, is selected from poly-chlorinated isocyanurates, polymeric polyisocyanate, isocyanic ester and their combination,
Wherein, described multipolymer has
The melt temperature of 100 ℃ to 120 ℃;
The number-average molecular weight of at least 30,000g/mol;
The limiting viscosity of at least 1.0 minutes Liter Per Minutes;
The Tg of-30 ℃ to-10 ℃, and
Described multipolymer comprises by the derivative residue of described polyethylene terephthalate component.
2. method according to claim 1, comprising:
(a), being enough to form under the condition of poly-(hexanodioic acid fourth diester) oligopolymer, under the existence of catalyzer, make BDO and hexanodioic acid reaction;
(b) be enough to described in depolymerization polyethylene terephthalate component to form under the condition of described poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer, in inert atmosphere, at the temperature of 190 ℃ to 270 ℃, in normal atmosphere or relative superiority or inferiority more, 1, under the existence of 4-butyleneglycol, in conjunction with described polyethylene terephthalate component and described poly-(hexanodioic acid fourth diester) oligopolymer; And
(c) mole number based on described catalyzer, to the phosphoric acid quencher that adds 0.05 to 1 molecular fraction in described poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) polymkeric substance.
3. method according to claim 1, comprising:
(a) being enough to the depolymerization of described polyethylene terephthalate component, be under the condition of the first molten mixture, under the existence of catalyst component, in normal atmosphere or higher reactor, make the following reaction:
(i) polyethylene terephthalate component, is selected from the group of polyethylene terephthalate, polyethylene terephthalate copolymer and their combination, with
(ii) diol component, is selected from ethylene glycol, propylene glycol and their combination; And
(b) being enough to form under the second molten mixture condition comprise oligopolymer, under the existence of catalyst component, in described molten mixture, add BDO and adipic acid; And
(c) mole number based on described catalyzer, to the phosphoric acid quencher that adds 0.05 to 1 molecular fraction in described poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer.
4. for the preparation of having 100 ℃ to the method for poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer of 120 ℃ of melt temperatures, described method comprises:
Being enough to form under the condition of poly-(hexanodioic acid fourth diester) oligopolymer, under the existence of catalyzer, make BDO and adipic acid reaction;
Be enough to described in depolymerization polyethylene terephthalate component to form under the condition of described poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer, in inert atmosphere, at the temperature of 190 ℃ to 270 ℃, in normal atmosphere or relative superiority or inferiority more, 1, under the existence of 4-butyleneglycol, in described poly-(adipic acid fourth diester) oligopolymer, add polyethylene terephthalate component;
Mole number based on described catalyzer, to the phosphoric acid quencher that adds 0.05 to 1 molecular fraction in described poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer; And
Be enough to form under the condition of described poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, described oligopolymer is reacted with the chainextender of 0.01 to 5 weight percentage, described chainextender is selected from poly-chlorinated isocyanurates, polymeric polyisocyanate, isocyanic ester and their combination, described poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer has the melt temperature of 100 ℃ to 120 ℃, and comprises by least one derivative residue of described polyethylene terephthalate component.
5. for the preparation of a method of gathering (terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer with the melt temperature of 100 ℃ to 120 ℃, described method comprises:
Being enough to the depolymerization of described polyethylene terephthalate component, be under the condition of the first molten mixture, under the existence of catalyst component, in normal atmosphere or higher reactor, make the following reaction:
(i) polyethylene terephthalate component, is selected from the group of polyethylene terephthalate, polyethylene terephthalate copolymer and their combination, with
(ii) diol component, is selected from ethylene glycol, propylene glycol and their combination;
Being enough to form under the condition of the second molten mixture comprise oligopolymer, under the existence of catalyst component, in described molten mixture, add BDO and oxalic acid;
Mole number based on described catalyzer, to the quencher that adds 0.05 to 1 weight percentage in described poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) oligopolymer; And
Be enough to form under the condition of described poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, described oligopolymer is reacted with the chainextender of 0.01-5 weight percentage, described chainextender is selected from chlorinated isocyanurates, polymeric polyisocyanate, isocyanic ester and their combination, described poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer has the melt temperature of 100 ℃ to 120 ℃, and comprises by the derivative residue of described polyethylene terephthalate component.
6. according to method in any one of the preceding claims wherein, wherein, described poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer has at least 30,000 molecular weight; The I.V. of at least 1.0 minutes Liter Per Minutes; And the Tg of-30 ℃ to-10 ℃.
7. according to method in any one of the preceding claims wherein, wherein, the total mole number based on terephthalic acid, hexanodioic acid and Isosorbide-5-Nitrae butyleneglycol, the amount of described quencher is 0.05 to 1 molecular fraction.
8. according to method in any one of the preceding claims wherein, wherein, described quencher is selected from phosphoric acid, phosphorous acid, boric acid, nitrogenous compound and their combination.
9. according to method in any one of the preceding claims wherein, wherein, described chainextender is selected from monokaryon isocyanic ester, double-core isocyanic ester, three core isocyanic ester, four core isocyanic ester or higher core isocyanic ester and their mixture, in free following the formed group of vulcabond choosing: Toluene-2,4-diisocyanate, 4-vulcabond, Toluene-2,4-diisocyanate, 6-vulcabond, 2, 4'-diphenylmethanediisocyanate, naphthylidene-1, 5-vulcabond, xylylene vulcabond, hexamethylene diisocyanate, isophorone diisocyanate and methylene-bis (2-cyclic isocyanate hexane).
10. method according to claim 9, wherein, described chainextender is combination, the gross weight based on described combination, described combination comprises:
The chainextender that is selected from the following of 45 to 80 weight percentage: monokaryon chlorinated isocyanurates, the chainextender that contains two functional groups of reacting with the end group of described oligopolymer or their combination;
The chainextender that is selected from the following of 13 to 25 weight percentage: double-core chlorinated isocyanurates, the chainextender that contains three functional groups of reacting with the end group of described oligopolymer and their combination;
The chainextender that is selected from the following of 5 to 12 weight percentage: three core chlorinated isocyanurates, the chainextender that contains four functional groups of reacting with the end group of described oligopolymer and their combination; And
Four core chlorinated isocyanurates of 2 to 18 weight percentage or higher core chlorinated isocyanurates.
11. according to method in any one of the preceding claims wherein, wherein, described glycol is selected from ethylene glycol, 1,2-propylene glycol, 1,3-PD, 1,2-butyleneglycol, 2,3-butyleneglycol, 1,4-butyleneglycol, tetramethylcyclobutanediol, Isosorbide, hexylene glycol, 1,3-CHDM isomer, 1,4 cyclohexane dimethanol isomer, biologically-derived glycol or their combination.
12. according to method in any one of the preceding claims wherein, and wherein, described glycol is selected from BDO, 1,3-PD, ethylene glycol and their combination.
13. according to method in any one of the preceding claims wherein, wherein, described aromatics dicarboxylic compounds is selected from terephthalic acid or its two (C1-3) alkyl ester, m-phthalic acid or its two (C1-3) alkyl ester, naphthalic acid or its two (C1-3) alkyl esters and their combination.
14. according to method in any one of the preceding claims wherein, and wherein, described aromatic dicarboxylic acid compound is terephthalic acid or its two (C1-3) alkyl ester.
15. according to method in any one of the preceding claims wherein, wherein, described polyester components residue comprises the residue of dimethyl isophthalate, cyclohexanedimethanol, ethylene glycol, glycol ether, triglycol, ethylene glycol group, diethylene glycol group, m-phthalic acid group and their combination.
16. 1 kinds of poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymers with the melt temperature of 100 ℃ to 120 ℃, wherein
Described multipolymer comprises the residue being derived by polyethylene terephthalate component, and described polyethylene terephthalate component is selected from polyethylene terephthalate, polyethylene terephthalate copolymer and their combination;
Quencher residue; And
The residue of the chlorinated isocyanurates of 0.05 to 1 weight percentage, polymeric polyisocyanate, isocyanic ester and their combination.
17. multipolymers according to claim 16, based on poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, the described quencher residue that comprises 0.05 to 1 molecular fraction.
18. according to the multipolymer described in claim 16 or 17, and wherein, the described described residue being derived by polyethylene terephthalate component is selected from ethylene glycol group, diethylene glycol group, m-phthalic acid group and their combination.
19. according to multipolymer in any one of the preceding claims wherein, and wherein, based on poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, described multipolymer comprises the ethylene glycol group that is less than 10 molecular fractions.
20. according to multipolymer in any one of the preceding claims wherein, and wherein, based on poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, described multipolymer comprises the m-phthalic acid ester group that is less than or equal to 2 molecular fractions.
21. according to multipolymer in any one of the preceding claims wherein, wherein, and based on poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymer, the combination that described multipolymer comprises the ethylene glycol group and the m-phthalic acid ester group that are less than 10 molecular fractions.
22. 1 kinds of compositions, comprise:
According to poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) in any one of the preceding claims wherein multipolymer; And
At least one
Be selected from the additive of the following: nucleator, antioxidant, UV stablizer, softening agent, epoxy compounds, melt strength additive, alcohol, acetic ester, alcohol-acetate copolymer, linking agent, antiaging agent, aging dose, antiblocking agent, water, odor control agent and their combination; And
Other thermoplastic polymer.
23. compositions according to claim 22, comprise:
Gross weight based on described composition, is greater than described poly-(terephthalic acid-altogether-hexanodioic acid fourth diester) multipolymers of 10 to 59.99 weight percentage;
Gross weight based on described composition, be greater than 40 to the polymkeric substance that is less than 89.99 weight percentage, described polymkeric substance is selected from aliphatic polyester, aliphatic polycarbonate, starch, aromatic polyester, present cycloaliphatic polyesters, polyesteramide, aromatic polycarbonate and their combination; And
Gross weight based on described composition, the additive that is selected from the following of 0.01 to 5 weight percentage: nucleator, antioxidant, UV stablizer, softening agent, epoxy compounds, melt strength additive and their combination;
Gross weight based on described composition, the additive that is selected from the following of 0.01 to 45 weight percentage: alcohol, acetic ester, alcohol-acetate copolymer and their combination; And
Weight based on described composition, the additive that is selected from the following of 0.01 to 2 weight percentage: linking agent, antiaging agent, aging dose, antiblocking agent, water, odor control agent and their combination.
24. according to the composition described in claim 22 or 23, wherein, described aliphatic polyester is selected from poly-(lactic acid) class, poly-(hydroxyalkanoate) class, poly-(succinic acid fourth diester) class, poly-(hexanodioic acid fourth diester) class, poly-(succinic acid hexanodioic acid fourth diester) class, poly-(caprolactone) class and their combination.
25. 1 kinds comprise according to the goods of the composition described in claim 22,23 or 24.
26. goods according to claim 25, wherein, described goods are moulded product, film, fiber or coating.
27. 1 kinds of methods that form goods, comprise molding, coating, calendering, moulding or extrude the composition described in claim 22,23 or 24.
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